Autogenous shrinkage in high-performance cement paste: An evaluation of basic mechanisms

In this paper, various mechanisms suggested to cause autogenous shrinkage are presented. The mechanisms are evaluated from the point of view of their soundness and applicability to quantitative modeling of autogenous shrinkage. The capillary tension approach is advantageous, because it has a sound mechanical and thermodynamical basis. Furthermore, this mechanism is easily applicable in a numerical model when dealing with a continuously changing microstructure. In order to test the numerical model, autogenous deformation and internal relative humidity (RH) of a Portland cement paste were measured during the first week of hardening. The isothermal heat evolution was also recorded to monitor the progress of hydration and the elastic modulus in compression was measured. RH change, degree of hydration and elastic modulus were used as input data for the calculation of autogenous deformation based on the capillary tension approach. Because a part of the RH drop in the cement paste is due to dissolved salts in the pore solution, a method is suggested to separate this effect from self-desiccation and to calculate the actual stress in the pore fluid associated with menisci formation.     

Autogenous relative humidity change and autogenous shrinkage of high-performance cement pastes

In this paper, the effects of water to cementitious material ratio (w/cm), silica fume (SF) and ground blast-furnace slag (GBFS) on autogenous relative humidity (RH) change and autogenous shrinkage (AS) of high-performance cement pastes were studied. The mechanism of self-desiccation caused by mineral admixture and reduction of w/cm were studied by the parameters of mineral admixture self-desiccation-effect coefficient k and efficient w/cm r_e proposed. Furthermore, the relationship between autogenous RH and AS of high-performance paste was established. The results indicate that w/cm is a chief factor that affects autogenous RH change and AS of cement pastes. The lower the w/cm of paste is, the more reduction the autogenous RH and the increment of AS are. SF increases autogenous RH reduction and AS increment of cement paste at early ages, and GBFS increases autogenous RH reduction and AS increment at later ages. The effect of mineral admixtures on autogenous RH change of paste resulting from self-desiccation can be reflected effectively by the nonlinear equation with the parameters of k and r_e. There exists a good linear correlation between autogenous RH change and AS of cement pastes.     

Experimental study of gas diffusion in cement paste

This paper presents an experimental study of gas diffusion in binary mixtures of hydrogen-nitrogen and xenon-nitrogen through cement pastes (CEM I and CEM V) of different water/cement ratios (0.35 and 0.45). First, the impact of water saturation on gas diffusion is investigated by performing tests on samples pre-conditioned in specific atmospheric conditions (dry, 55, 70, 82, 93 and 100% RH) by means of saline solutions. The comparison of the results obtained for the CEM I and the CEM V samples (w/c ratio of 0.45) demonstrate the importance of pore size distribution/connectivity on gas diffusion. Second, diffusion tests at different total pressures and using two different mixtures (hydrogen-nitrogen, xenon-nitrogen) are performed to study the nature of gas diffusion in cement paste. Results demonstrate that gas diffusion in cement paste is controlled by Knudsen and ordinary diffusion at pressures greater than 100 kPa and mainly by Knudsen diffusion at pressures less than 100 kPa.     

Effect of relative humidity decrease due to self-desiccation on the hydration kinetics of cement

Hydration rate of cement decreases at reduced relative humidity (RH) and hydration virtually ceases below about 80% RH. Until now, this problem has been studied by means of determining the hydration degree only at later ages on hydrated samples continuously stored under fixed, reduced RH, or based on theoretical considerations. Here, the effect of reduced RH on hydration rate was studied in the course of the process during initial days of hydration. Isothermal calorimetry was applied to study the evolution of the heat of hydration in cement pastes with low water-to-binder ratio, either in water-saturated or sealed conditions. In parallel, RH evolution was measured on sealed, companion samples with water-activity stations. The sealed samples show considerably lower rates of hydration when the RH is reduced due to self-desiccation. The coefficient describing the reduction of hydration rate as a function of RH was determined for different water-to-binder ratios and different cements.     

On the mechanism of polypropylene fibres in preventing fire spalling in self-compacting and high-performance cement paste

With the increasing application of self-compacting concrete (SCC) in construction and infrastructure, the fire spalling behavior of SCC has been attracting due attention. In high performance concrete (HPC), addition of polypropylene fibers (PP fibers) is widely used as an effective method to prevent explosive spalling. Hence, it would be useful to investigate whether the PP fibers are also efficient in SCC to avoid explosive spalling. However, no universal agreement exists concerning the fundamental mechanism of reducing the spalling risk by adding PP fiber. For SCC, the reduction of flowability should be considered when adding a significant amount of fibres.In this investigation, both the micro-level and macro-level properties of pastes with different fiber contents were studied in order to investigate the role of PP fiber at elevated temperature in self-compacting cement paste samples. The micro properties were studied by backscattering electron microscopy (BSE) and mercury intrusion porosimetry (MIP) tests. The modification of the pore structure at elevated temperature was investigated as well as the morphology of the PP fibers. Some macro properties were measured, such as the gas permeability of self-compacting cement paste after heating at different temperatures. The factors influencing gas permeability were analyzed.It is shown that with the melting of PP fiber, no significant increase in total pore volume is obtained. However, the connectivity of isolated pores increases, leading to an increase of gas permeability. With the increase of temperature, the addition of PP fibers reduces the damage of cement pastes, as seen from the total pore volume and the threshold pore diameter changes. From this investigation, it is concluded that the connectivity of pores as well as the creation of micro cracks are the major factors which determine the gas permeability after exposure to high temperatures. Furthermore, the connectivity of the pores acts as a dominant factor for temperatures below 300 °C. For higher temperatures micro cracks are becoming the major factor which influences the gas permeability.     

X-ray absorption study of drying cement paste and mortar

X-ray absorption was used to observe water evaporation with hydration time in paste and mortar specimens, with the aim of studying the influence of water/cement (w/c) ratio, presence of aggregates, curing conditions on drying during early hydration. For the samples subjected to surface drying immediately after mixing, there exists a moisture gradient within the internal part of the specimen. However, obvious top-down drying only occurs within a small zone near the surface for early age cement pastes and mortars. The evaporation rate of water is very high in the first day after casting and is drastically reduced afterwards due to the formation of a microstructure that greatly improves specimens resistance to moisture loss. Mortars reveal a slightly lower evaporation rate since the aggregate increases the length of the transport route because of a larger tortuosity. However, the effect of sealed curing is much more important than the tortuosity effect of the aggregates.     

ESEM analysis of polymeric film in EVA-modified cement paste

Portland cement pastes modified by 20% weight (polymer/cement ratio) of poly(ethylene-co-vinyl acetate) (EVA) were prepared, cured, and immersed in water for 11 days. The effects of water saturation and drying on the EVA polymeric film formed in cement pastes were observed using environmental scanning electron microscopy (ESEM). This technique allowed the imaging of the EVA film even in saturated samples. The decrease of the relative humidity inside the ESEM chamber did not cause any visual modification of the polymeric film during its drying.     

Local porosity analysis of pore structure in cement paste

Three-dimensional (3-D) local porosity theory (LPT) was originally proposed by Hilfer and recently used for the analysis of pore space geometry in model sandstone. LPT pursues to define the probability density functions of porosity and porosity connectivity. In doing so, heterogeneity differences in various sandstone samples were assessed. However, fundamental issues as to the stochastic concept of geometric heterogeneity are ignored in Hilfer's LPT theory. This paper focuses on proper sampling procedures that should be based on stochastic approaches to multistage sampling and geometric heterogeneity. Standard LPT analysis provides a 3-D microscopic modeling approach to materials. Traditional experimental techniques yield two-dimensional (2-D) section images, however. Therefore, this paper replaces the method for assessing material data in standard LPT theory to a more practical one, based on stereological, 3-D interpretation of quantitative image analysis data. The developed methodology is used to characterize the pore structure in hardened cement paste with various water/cement ratios (w/c) at different hydration stages.     

Rheological properties of cement paste: Thixotropic behavior and structural breakdown

In this work, a new material model is presented to simulate rheological behavior of cement paste. This material model is among others based on combined concepts by Hattori and Izumi and by Tattersall and Banfill. More precisely, coagulation, dispersion and re-coagulation of the cement particles (giving a true thixotropic behavior) in combination with the breaking of certain chemically formed linkages between the particles (giving a so-called structural breakdown behavior) are assumed to play an important role in generating the overall time-dependent behavior of the cement paste. The model evaluation is done by comparing experimental data with model prediction.     

Transport of a surface-applied corrosion inhibitor in cement paste and concrete

Surface-applied corrosion inhibitors are a kind of repair material and usually contain an aminoalcohol and a component forming a salt with the aminoalcohol. According to the manufacturers, this type of inhibitor penetrates very rapidly into concrete; however, the transport mechanisms have not been sufficiently investigated so far. The major part of the study therefore focused on the transport of the ingredients of an inhibitor in cement paste and concrete, which contained an aminoalcohol and a phosphorous compound. It has been shown that the latter forms an insoluble calcium salt in the environment of cement and precipitates quantitatively. It is thus unable to penetrate from the outside into the alkaline concrete zone and cannot develop its inhibiting effect there. The aminoalcohol, on the other hand, is not bound by cement, but remains largely dissolved in the pore liquid, thus providing optimal conditions for high mobility. The analysis of the transport mechanisms involved has revealed that diffusion in the dissolved state is by far the most efficient transport mechanism. While basically the transport of the aminoalcohol via the gaseous phase is possible, it does play an inferior role only. Surprisingly, the substance had hardly been absorbed by concrete by capillary suction, but at first remained close to the concrete surface.     

Performance of new viscosity modifying admixtures in enhancing the rheological properties of cement paste

The use of viscosity modifying admixtures (VMA) has proved to be very effective in stabilizing the rheological properties and consistency of self-compacting concrete (SCC). SCC is known for its excellent deformability, high resistance to segregation and use, without applying vibration, in congested reinforced concrete structures characterized by difficult casting conditions. Most of the commercial VMAs currently available in the market are costly and increase the price of such a concrete. Identification or production of new low-cost VMA is then essential. This paper presents the performance of four new polysaccharide-based VMAs in enhancing the rheological and consistency properties of cement paste. The study of the rheological properties and consistency of cement paste to screen the dosage and type of new VMA to be used in SCC is a promising approach. Investigation was carried out on cement pastes with combinations of various dosages of new VMAs and of a superplasticizer (SP) to study the influence on rheology, consistency and washout mass loss. A commercial VMA designated in this paper as “COM” was tested for comparison. The study on new VMAs is encouraging and confirms that pastes with satisfactory rheological and consistency properties comparable with or even better than commercial VMA can be developed. The combined use of proper dosages of VMA and SP is shown to clearly contribute to securing high-performance cement pastes that is highly fluid yet cohesive enough to reduce water dilution and enhance water retention. Attempt has also been made to correlate rheological properties (yield stress) to consistency (slump) of pastes.     

On the mechanism of strength enhancement of cement paste and mortar with triisopropanolamine

Recent work on the strength-enhancing mechanism of triisopropanolamine (TIPA) suggested that TIPA enhances the mechanical properties of mortar and concrete by acting on the interfacial transition zone (ITZ) between paste and sand or aggregate rather than improving the properties of the hydrated binder. This paper presents compressive strength data for 10 Portland cements tested as cement paste as well as two different kinds of mortar after 28 days hydration, so that these two mechanisms could be compared directly. The average strength improvement with TIPA was 10% in the hydrated portland cement paste and 9% in the mortar, clearly showing that the strength enhancement is not dependent on an ITZ mechanism.     

Measuring permeability and stress relaxation of young cement paste by beam bending

When a saturated rod of a porous material is deflected in three-point bending, two types of time-dependent relaxation processes occur simultaneously: hydrodynamic relaxation, caused by the flow of liquid in the porous body, and viscoelastic (VE) relaxation of the solid network. By measuring the decrease in the force required to sustain a constant deflection, it is possible to obtain the permeability from the hydrodynamic relaxation function, in addition to the VE stress relaxation function of the sample. We report the early-age evolution of permeability, elastic modulus, and stress relaxation function for Type III Portland cement paste with water–cement (w/c) ratios of 0.45, 0.50, and 0.55. The stress relaxation function is shown to preserve its shape during aging; that function is numerically transformed into the creep function.     

Early-age acoustic emission measurements in hydrating cement paste: Evidence for cavitation during solidification due to self-desiccation

In this study, the acoustic emission activity of cement pastes was investigated during the first day of hydration. Deaired, fresh cement pastes were cast in sealed sample holders designed to minimize friction and restraint. The majority of acoustic emission events occurred in lower water to cement ratio pastes, while cement pastes with higher water to cement ratios showed significantly less acoustic activity. These acoustic events occurred around the time of setting. A layer of water on the surface of the cement pastes substantially reduced acoustic emission activity at the time of setting. According to these experimental results, the acoustic emission measured around setting time was attributed to cavitation events occurring in the pores of the cement paste due to self-desiccation. This paper shows how acoustic emission might be used to indicate the time when the fluid–solid transition occurs in a cement paste, often referred to as time-zero. Knowledge of time-zero is fundamental for determining when mechanical properties develop and in calculations of residual stresses.     

Suspended hydration and loss of freezable water in cement pastes exposed to 90% relative humidity

Degree of hydration (DOH) and differential scanning calorimetry (DSC) measurements are used to characterize the effect of early exposure to a 90% relative humidity (RH) environment on cement paste hydration. Early exposure to a 90% RH environment can lead to the consumption of freezable water and altered microstructural development. The minimum duration of 100% RH curing required to eliminate the effects of an unsaturated environment on microstructural development coincides with the appearance of a DSC peak near −30 °C that occurs in the range 1-14 days for the pastes studied. The Jennings colloidal microstructural model is used to argue that the −30 °C peak coincides with the cessation of capillary pore percolation. Alternatively, all samples cured under 100% RH conditions for 7 days prior to 90% RH exposure hydrated at the same rate as those continuously exposed to 100% RH. The application of these results to the formulation of separate curing practices for durability and strength is discussed.     

Rehydration and microstructure of cement paste after heating at temperatures up to 300 °C

This paper is concerned with the evolution of the microstructure of cementitious materials subjected to high temperatures and subsequent resaturation in the particular context of long-term storage of radioactive wastes, where diffusive and convective properties are of primary importance. Experimental results obtained by mercury intrusion porosimetry (MIP) are presented concerning the evolution of the pore network of ordinary portland cement (OPC) paste heated at temperatures varying between 80 and 300 °C. The consequences of heating on the macroscopic properties of cement paste are evaluated by measures of the residual gas permeabilities, elastic moduli and Poisson's ratio, obtained by nondestructive methods. Resaturation by direct water absorption and water vapour sorption are used to estimate the reversibility of dehydration. The results provide some evidence of the self-healing capacity of resaturated cement paste after heating at temperatures up to 300 °C.     

Relationship between the surface free energy of hardened cement paste and chemical phase composition

Special emphasis is put on to correlating the changes in phase composition with wettability of hardened cement paste. The results were found in contradiction, because it was demonstrated by XRD analysis that by increment in curing ages, high energy products are developed in the matrix which increases surface free energy. In contrast, surface evaporation of the water and bulk hydration cause a decrease in hydrophilic properties of the surface free energy. It was concluded that the latter phenomenon has more important impact than surface free energy.     

Possibilities of using the ultrasonic wave transmission method to estimate initial setting time of cement paste

In this paper, the applicability of the ultrasonic wave transmission method to estimate the initial setting time of an arbitrary cement paste is discussed. Ultrasonic pulse velocity measurements were fully automated and measured continuously. The Vicat Needle Test was used in order to determine the initial setting time of cement pastes. Different cement pastes were prepared in order to check the influence of the water/cement ratio, type of cement, curing temperature, cement fineness, and some clinker compositions, on the relationship between the initial setting time and ultrasonic pulse velocity. It was found that the initial setting time of an arbitrary cement paste can be estimated very accurately by the time the first inflection point appears on the ultrasonic pulse velocity curve. Moreover, it can be estimated quite accurately by the time the ultrasonic pulse velocity reaches a fixed value, close to the value of the ultrasonic pulse velocity in water.     

Development of technique for observing pores in hardened cement paste

Mercury intrusion porosimetry is a widely used technique to determine the pore size distribution in porous materials. However, this technique does not provide information about the shapes and locations of pores. A new technique is developed, in which gallium (Ga) is used as an alternative intrusion liquid because of its property of being solid at normal room temperature (melting point: 29.8 °C). This permits the examination of pores using image analysis. The technique is applied to hardened cement paste. The distribution of solid Ga is observed through an electron probe microanalyzer (EPMA), and the shapes and locations of pores in cement paste are discussed.     

Change in pore structure and composition of hardened cement paste during the process of dissolution

An understanding about the dissolution phenomena of cement hydrates is important to assess changes in the long-term performance of radioactive waste disposal facilities. To investigate the alteration associated with dissolution, dissolution tests of ordinary Portland cement (OPC) hydrates were performed.Through observation of the samples after leaching, it was confirmed that ettringite precipitation increased as the dissolution of the portlandite and the C-S-H gel progressed. EPMA performed on cross-sections of the solid phase showed a clear difference between the altered and unaltered parts. The boundary between the two parts was termed the portlandite (CH) dissolution front. As the leaching period became longer, the CH dissolution front shifted toward the inner part of the sample. A linear relationship was derived by plotting the distance moved by the CH dissolution front against the square root of the leaching time. This indicated Ca ion movement by diffusion.